Stabilized ice color composition



Patented 25, 1944 s'raamrzsn ICE COLOR cosmosrrrom CONTAINING BIGUANIDEPaul P. McClellan, Old Greenwich, and Walter P. i Ericks, Cos Cob,Conn., assi'gnors to American Cyanamid Company, New York, N. Y., acorporation of Maine I No Drawing.

This invention relates to a new class of chemical' compoundstointermediates and dyes obtalned therefrom, and to their methods ofpreparation.

vThe principal object of this invention'is to prepare new stabilizeddiazo compounds, preferably those soluble in water and in the morecommonly used organic solvents.

Application August 30, 1941, Serial No'. 409,064

6 Claims.

. Among the stabilized diazo compounds included herein are, moreespecially, the reaction products of an ice color diazo component withan alkylol or an alkoxyalkylol derivative of himnide. Inasmuch as thesederivatives, each exist in several tautomeric forms, the reaction prod-.ucts prepared from any one may occur as a mixture of isomers whichreadily undergo rearrangement. Hence',,- assignment of a definitechemical formula is problematical.

However,.the chemical properties of the products and the particularmethod or methods of preparation disclosed herein cause one of theisomers to appear in excess, and under the present conditions "themonomeric form is produced predominantly. Thus the alkylol andalkoxyalkylol biguanide probably give:

. H n RN=N-1 r c-Nn-c- I \r-R. s H in which R represents the nucleus ofan aromatic amine such as the nucleus of, an ice color diazocomponent;and R2 is an alkylol or alkoxyalkylol E OUP- These stabilized diazocompounds are resistant to percussion and even when heatedin a directflame decompose without the hazard of an explosion. when in a drycondition or in an alkaline solution they are stable at temperaturesencountered throughout all seasons of the year, and

hence may be stored indefinitely. However, these reaction productspossess the property of splitting into their original components bytreatment with acids at elevated temperatures or with steam containingvolatile acid vapors. If this splitting occurs in the presence of an icecolor. coupling qomponent, the regenerated active .diazotized componentbecomes available immediately for revention' to prepare new azo pigmentsand dyes action with the coupling component and produces thecorresponding azo pigment or dye.

To this end it is a further object of this iny mlzinlanice colorcoupling component and the reaction product of an ice color diazocomponent with an alkylol or alkoxyalkylol dcriva- I8 tive ofbiguanide.- As such, the mixture may or may not be colored. However, ifa textile material is printed or impregnated with this mixture and thenheated in the presence of an acid, the acid hydrolyzes the stable diazocompound, splitting it into its components; and the regenerateddiazotized component liberated couples with the ice color couplingcomponent to form an azo pigment or dye.

This acid treatment or ageing as it is called,

is preferably efiected with a weak acid and at an elevated temperature.Usually formic or acetic acids are used, but variousother acids as wellas substances liberating acids upon being steamed such as ammoniumsulfate, esters of' tartaric, s'uccinic, etc., acids may 'beusedparticularly when the printed material is subjected to'a subsequentsteam treatment to efiect ageing or develop the color.

Stable alkaline printing pastes can be prepared from the mixture of theice color couplin component and the reaction product of the ice colordiazo component with one of the alkylol or alkoxyalkylol derivatives bydissolving the mixture in a solvent such as water, alcohol, acetone,, I

etc., together with various other ingredients such as alkalies, organicbases, impregnating agents,

thickeners such as starch, gum, etc., well known' to those'skilled inthe art. .Cotton goods can be printed with this paste with the aid of acopper roll. The print is then dried and subsequently the desired coloris developed by steaming in the'presence of acetic acid or othervclatile acid vapors. In this manner an insoluble azo pigment isproduced in and on the cotton fibers in the form of the printed pattern.Such prints are bright and possess remarkable fastness to light andwashing.

The facility with which the compounds and dyes included in thisinvention can be 'used is based upon theease withwhich the stabilizeddiazamino group present can be split and'con- 'verted inl ii an activediazo group by heating in the presence of an acid or an acid liberatingsubstance. -'lhis conversion or ageingis usually enacted in a steamchamber and in the presence or a coupling component. Under these con:ditions the active diazo group is free for such a short time intervalthat .it does not decompose and instead couples with the couplingcomponent (e. g. naphthol in one of the examples given below) to developor form the color.

The following examples describe the -prepara-.

tion of several stabilized diazo compounds included in this inventionand further give details as to their dyeing and printing textile masa mbicuanide reacted with. -tczuume alazonium hydrochloride. 'An aqueoussolution of biguanide was prepared by reacting 18.25 g. of blguanidesulfate. 8.8 g. of sodium hydroxide and 28.8 g. of sodium carbonate in100 cc. of water. The solution was cooled with'loo g. of ice and 7.7 g.of p-toiuidine diazonium. chloride was added to the biguanide solutionwith constant stirring. A

Y bright yellow precipitate was formed, filtered off and the filter cakedried at room temperature to yield a brown powder. This stabilized diazocompound was slurriedin an alkaline aqueous solution, cooled to 5-10" C.with ice and then reacted with 2.7 g. of ethylene oxide introducedslowly and with constant stirring until all of the stabilized dlazocompound was in solution.

This solubilized diazo compound has the following probable formula:

HiOON=N-lI-?NE-F-N-CHaCHaO v sln its Any one of a number oi. couplingcomponents known to those versed in the art can be admixed with thisdiazo compound, such as 1- naphthol, the o-toluidide oi2,3-hydroxy-naphthoic acid, the 2,5-dimethoxy anilide of 2,3-hydroxy-naphthoic acid, or the 4-chloranilide of 2,8-hydroxy-na'phthoicacid. For example, the

above prepared solution of the stabilized diazo' compound mixed with2,5-dimethoxy anilide of 2,8-hydroxynaphthoic acid was stable inelkaline "solution but quickly formed a .red dye upon acidifying andheating the mixture.

Exmu: It

when the stabilized diazo compound of Example I was reacted withglycidol in an aqueous solution to which some sodium hydroxide had beenadded, a stabilized diazo compound was obtained having the followingprobable formula:

I It was soluble in water forming a stable solution. However when mixedwith a coupling component free of solubilizinggroups (such as analkaline alcohol water solution of sodium a-naphtholate), acidified andheated, a water insoluble organic pigment is formed.

Similarly various other members of the alkylol and alkoxyalkylol seriesor derivatives of biguanide may be obtained by using as a startingmaterial the corresponding compound containing a reactive ethylene oxidering and a corresponding substituent in the ethylene oxide ring. Thusinstead of ethylene oxide, one or more mol. of glycidol, propyleneoxide, isopropylene oxide butylene oxide, isobutylene oxide, etc., etc.,can be used in order to render the stabilized diazo compound watersoluble. A number of such compounds are described in the copendingapplications Serial Numbers 289,398 and 289,400 of Walter P. Ericka.

It is to be particularly noted that although for ease of description,the aromatic amine chosen in the examples illustrating specificembodiments of the invention was p-toluidine, various other stable diasocompounds embraced assaoas herein can he' -prepared from-practically anyfee color diazo component. Thus other typical amines which can bediazotized and reacted with the stabilizing components include inaddition to p-toluidine, among numerous others familiar to thoseversed'in the art, aniline aswell as homologues of aniline, namely2,4-dimethylaniline; Where still other color 'variations are desired,the. halogen derivatives of aniline may be used, such as themonochloroanilines, dichloranilines; anilines substituted by hydrocarbonradicals; such as alkyl, alkoxy radicals, for'=l example methyl, ethyl,etc., methoxy, ethoxy, etc; or anilinessubstituted' by nitro radicals,acyl derivatives thereof, and the like.

Similarly, although l-naphthol is given as the most frequently usedcoupling component for the dye mixture incorporating the specificstabilised strued broadly and limited solely as defined by the scope ofthe appended cl We claim:

1. A color producing composition or matter which comprises an ice colorcoupling component and a stabilized diazo compound having the tormula;

R-N= -N-c-N n-c-1 rn,

in which R. is thenucleus of an ice color dlazo component of the benzeneseries and Rs is selected from the group consisting of an alkylol and analkoxyalkylol group.

2. A color producing composition of matter which comprises an ice colorcoupling component and a stabilized diam-compound havin the formula:

in which R is the nucleus or an ice color diaso h'lH 11m component ofthe benzene series and x is a saturizged aliphatic radical having atleast two carbon a ms.

3. A stabilizedoiazo compound having the formula:

R-N= -N-ICNH?-I ICHaCHaO'H in which R is the nucleus of an ice colordiazo I component of the benzene series.

4. A stabilized diazo compound having the formula:

R-N= N(|JNH(|3I I.CHaCHCH|0H 1th a ninwhichRis'thenucleusofanicecoloi-diasocomponent of the bensene series.

5. A method of coloring material comprising the application to thematerial or a mixture of an ice color coupling component and astabilized diazo component having the formula:

va ed mperature.

8. A printing paste comprising a printinx Jv I 3 thickener-associatedwith a mixture 0! an ice color coupling component and a reaction productof anice color diazo component with a stabilized diazo compound havingthe formula:

m which R is the nucleus of an icecolor diazo component oi the benzeneseries and R: is selected from the group consisting of an-alky1ol and analkoxyalkylol group.

PAUL P. MOCLEILAN. WALTER P. ERICKB.

